SUPPLEMENTARY MATERIAL to Geochemical Investigation As a Tool

J. Serb. Chem. Soc. 80 (8) S278–S285 (2015) Supplementary material

SUPPLEMENTARY MATERIAL TO Geochemical investigation as a tool in the determination of the potential hazard for soil contamination (Kremna Basin, Serbia) TAMARA PERUNOVIĆ1, KSENIJA STOJANOVIĆ1*#, MILICA KAŠANIN-GRUBIN2, ALEKSANDRA ŠAJNOVIĆ2#, VLADIMIR SIMIĆ3, BRANIMIR JOVANČIĆEVIĆ1# and ILIJA BRČESKI1 1University of Belgrade, Faculty of Chemistry, Studentski trg 12–16, 11000 Belgrade, Serbia, 2University of Belgrade, Center of Chemistry, ICTM, Njegoševa 12, 11000 Belgrade, Serbia and 3University of Belgrade, Faculty of Mining and Geology, Djušina 7, 11000 Belgrade, Serbia J. Serb. Chem. Soc. 80 (8) (2015) 1087–1099

AREA AND SAMPLING LOCATION The Kremna Basin covering an area of 15 km2 is a lacustrine basin of the Zlatibor complex and is located in southwest Serbia, about 200 km from Bel- grade (Fig. S-1). Zlatibor Mountain is one of the largest serpentinite massifs on the Balkan Peninsula and is an ecologically exceptional area with 960 plant species, 280 insect species, 10 amphibians and reptiles, 150 bird species and 54 mammal species.1 Kremna Basin landscape is hilly–mountainous with pastures, meadows and agriculture as the dominant vegetation type (Fig. S-1). The area is sparsely popul- ated with mountain villages, which are dispersed and mostly isolated. The main water supplies for the villages are springs. Due to its very interesting geological setting, this basin has been explored for magnesites and borates. During the last few decades, the Kremna Basin was stu- died for presence of searlesite in the magnesite deposit,2 magnesite and dolo- mite3,4 and sepiolite and palygorskite clays.5 The total thickness of sediments is about 350 m, and their age is of Lower Miocene, between 19 and 17 Ma.6,7 Obradović and Vasić (2007)8 distinguished two main sedimentation series, alluvial and lacustrine, and the latter was further divided into marginal and intrabasinal facies. The alluvial series consists of conglomerates and sandstones containing fragments of ultramafic rock,8 while the marginal lacustrine and intrabasinal lacustrine facies consists of carbonate sediments.9

* Corresponding author. E-mail: [email protected]; [email protected] S278

Fig. S-1. Locations in the Kremna Basin, borehole ZLT-2, reference soil samples and soil samples (1–7).

Pedogenic factors influenced the formation of humus silicate soil type on serpentinites in the Zlatibor region.10 These soils vary in color from black to brown with a dominant silt component and fairly stable aggregates.11 The humus silicate soils in the investigated area are shallow with depth varying between a few cm up to 20–30 cm. Usually only the A–R profile is developed on these soils, but the A–AC–R profile can also really be observed. There were two main criterions for soil sampling location: proximity to the borehole and outcropping sediments bellow soil. Only seven locations filled one or both of these criterions (Fig. S-1; Table I). Soil sample 1 was taken above the outcropping coal layer about 1.4 km north from the borehole site ZLT-2. At this location, the soil is very thin, up to 10 cm. Samples 2, 3 and 4 were taken in the central part of the basin, close to the location of the borehole ZLT-2. Sample 2 was taken 20 m west from the borehole, sample 3, 30 m east from the borehole, and sample 4 at the borehole site. Sample 5 was taken about 600 m, and sample 6 about 1 km northwest from the borehole site. Both soils are thin and light brown.

Sample 7 was taken about 1 km west from the borehole site and it is darker with more organic matter present. The reference soil sample (Table I) was determined by a statistical method. The contents of trace elements in the reference soil sample were calculated based on data for sixty soil samples (at depths up to 30 cm) surrounding the Kremna Basin (Fig. S-1), reported by the Agency for Environmental Protection, the Ministry of Energy, Development and Environmental Protection of the Republic of Serbia,12 using the following approach: for every element the mean ±2 standard deviation were used to eliminate the top and bottom outlying data.13 For studying of the Kremna Basin sediments, 43 core samples (5–10 cm in length) were taken from the ZLT-2 borehole, located in the central part of the Basin (Fig. S-1), at depth from 11.5 to 343 m (Table S-I). The borehole samples were taken for two purposes. The first one was the reconstruction of the origin and geological evolution of the sediments based on the determination of the qualitative mineral composition, content of major and several trace elements, which are important for understanding sedimentation processes, as well as a detailed investigation of the sedimentary organic matter. These results are given in a previous paper.14 The second purpose of the sampling was to determine background levels of heavy metals in the Kremna Basin. For this purpose, the contents of heavy metals interpreted in this study (As, Cr, Cu, Hg, Ni, Pb and Zn) were determined, whereas the contents of the major elements used for the calculation of the weathering parameters were taken from a previous paper.14 As was already mentioned, this location was chosen due to its importance as a potential evaporite (magnesite) deposit and boron occurrence, as well as because of its proximity to the Tara National Park. In the ZLT-2 borehole, the Lower Miocene sediments are more than 340 m thick. The borehole ends in weathered serpentinite, which is characterized by the occurrence of rare fragments of serpentinite, sepiolite and small amounts of quartz and dolomite. Background levels of heavy metals in the Kremna Basin sediments were calculated using the same statistical method as for the reference soil sample.13

______Available on line at www.shd.org.rs/JSCS/ (CC) 2015 SCS. All rights reserved. SUPPLEMENTARY MATERIAL S281 1 TABLE S-I. Contents of heavy metals (mg kg-1) and several major compounds (%) in sediment samples from ZLT-2 borehole of the Kremna 2 Basin, reference standard values and values of weathering indices Sample Depth CPAa CIWb Litology As Cr Cu Hg Ni Pb Zn Al O CaO Na O P O No. m 2 3 2 2 5 % % 1 11.5 Clayey 18.50 103.77 8.59 0.05 159.86 1.21 9.10 0.94 8.88 0.12 0.01 82.49 70.20 carbonates 2 13.5 Clayey 11.90 117.28 12.50 0.03 179.07 0.91 8.07 1.02 22.19 0.09 0.01 87.21 77.33 carbonates 3 27 Marly 5.14 103.41 6.55 0.05 119.09 3.12 15.11 3.03 21.58 0.11 0.02 94.33 89.27 dolomite 4 32 Marly 3.13 48.42 4.04 0.04 45.29 1.72 10.11 1.87 22.43 0.11 0.01 91.09 83.64 dolomite 5 42.5 Marlstone 27.07 89.85 9.80 0.06 152.24 2.93 11.11 3.04 37.64 0.07 0.02 96.32 92.89 6 54 Silty Mg- 79.35 119.56 18.81 0.12 159.83 5.24 26.72 6.80 9.24 0.08 0.01 98.05 96.18 -marlstone 7 55.5 Marly 30.05 62.73 8.25 0.04 105.64 1.94 11.21 1.97 18.86 0.08 0.03 93.62 88.00 dolomite 8 64.5 Marly 6.64 6.88 1.91 0.02 22.62 0.50 4.02 0.61 23.15 0.08 0.01 82.25 69.86 dolomite 9 70 Marlstone 35.29 105.2810.67 0.08 114.07 5.03 17.44 6.04 27.70 0.06 0.01 98.35 96.76 10 78 Dolomitic 34.86 27.66 3.94 0.04 55.58 2.12 8.08 2.09 32.77 0.13 0.01 90.64 82.87 marlstone 11 80 Dolomitic 37.89 20.85 4.88 0.07 34.84 1.63 10.16 2.38 36.77 0.11 0.02 92.82 86.60 marlstone 12 83 Marlstone 35.42 48.88 5.21 0.09 43.27 2.96 17.35 3.31 41.81 0.15 0.04 92.92 86.78 13 96 Marlstone 64.70 90.49 13.12 0.10 136.83 3.66 20.35 3.18 42.84 0.13 0.11 93.60 87.98 14 111 Marlstone 47.50 48.61 7.31 0.08 75.52 2.64 12.18 2.59 36.33 0.14 0.15 91.72 84.70

3 TABLE S-I. Continued Sample Depth CPAa CIWb Litology As Cr Cu Hg Ni Pb Zn Al O CaO Na O P O No. m 2 3 2 2 5 % % 15 113 Marlstone 32.32 265.1217.74 0.06 156.11 8.97 24.47 5.46 35.35 0.20 0.04 94.21 89.05 16 127 Marlstone 31.41 195.3918.77 0.07 270.37 6.94 18.36 5.18 38.01 0.25 0.04 92.51 86.06 17 137.5 Marlstone 11.69 55.16 6.35 0.04 72.85 1.91 5.04 1.18 44.58 0.15 0.06 82.58 70.33 18 150 Marlstone 7.78 112.00 10.85 0.06 240.02 3.99 11.25 1.87 32.43 0.16 0.01 87.42 77.66 19 164 Marlstone 8.00 131.69 9.32 0.04 245.54 2.94 8.10 1.82 43.88 0.20 0.12 84.55 73.23 20 185 Dolomitic 4.55 76.05 7.58 0.03 75.18 1.82 10.11 1.04 29.38 0.23 0.07 73.13 57.65 marlstone 21 189.5 Dolomitic 9.06 130.86 9.36 0.04 174.05 2.72 13.09 1.39 26.89 0.22 0.05 79.22 65.59 marlstone 22 216 Silty Mg- 3.30 162.47 4.03 0.03 203.59 0.93 5.16 0.31 13.46 0.41 0.01 31.31 18.56 -marlstone 23 219 Marly 3.04 180.02 4.65 0.02 227.08 1.32 6.07 0.85 5.99 0.29 0.01 63.78 46.82 magnesite 24 224 Marly 11.60 323.14 10.27 0.02 440.66 2.77 12.32 1.79 17.10 0.45 0.01 70.62 54.58 dolomite 25 238 Mg-clay 10.19 87.11 1.80 0.01 261.33 10.40 23.34 4.89 2.36 1.24 0.01 70.54 54.49 26 243.5 Marly 2.44 138.93 4.97 0.04 189.85 1.12 9.14 0.94 6.29 1.19 0.01 32.58 19.46 magnesite 27 245 Marly 4.11 555.53 4.21 0.02 604.73 0.92 8.22 0.73 4.79 0.69 0.01 39.18 24.36 magnesite 28 248.3 Marly 1.63 208.73 4.37 0.02 276.49 1.02 6.10 0.66 6.50 2.28 0.01 14.99 8.10 magnesite 29 255 Marly 1.83 340.85 3.36 0.02 263.83 0.92 6.10 0.60 4.58 0.70 0.01 34.20 20.63 magnesite

______Available on line at www.shd.org.rs/JSCS/ (CC) 2015 SCS. All rights reserved. SUPPLEMENTARY MATERIAL S283 4 TABLE S-I. Continued Sample Depth CPAa CIWb Litology As Cr Cu Hg Ni Pb Zn Al O CaO Na O P O No. m 2 3 2 2 5 % % 30 258 Silty Mg- 14.23 1279.03 15.29 0.05 1989.27 4.46 29.74 3.40 6.15 1.71 0.01 54.71 37.66 marlstone 31 265 Marly 2.86 223.94 9.51 0.02 346.12 2.35 10.23 1.30 5.84 1.40 0.01 36.04 21.98 magnesite 32 283 Magnesitic 2.59 255.57 5.71 0.01 351.32 1.97 9.34 1.35 13.79 1.16 0.01 41.37 26.08 marlstone 33 286 Magnesitic 5.24 416.15 7.97 0.03 680.47 2.94 13.63 2.27 11.49 1.56 0.02 46.84 30.58 marlstone 34 297.5 Magnesitic 2.91 213.55 39.12 0.08 298.48 3.54 47.86 2.09 9.19 1.53 0.01 45.39 29.36 marlstone 35 309 Silty Mg- 6.64 534.03 11.39 0.03 971.31 5.06 27.42 4.62 9.25 2.23 0.02 55.79 38.68 marlstone 36 317.5 Magnesitic 7.76 339.77 7.76 0.04 456.86 2.79 13.45 2.19 12.59 1.45 0.01 47.93 31.52 marlstone 37 324 Silty Mg- 11.68 712.72 11.89 0.03 802.29 4.63 22.10 3.65 7.70 1.98 0.02 52.87 35.94 marlstone 38 329 Silty Mg- 6.92 753.14 13.84 0.04 891.39 4.93 23.06 4.05 10.76 1.83 0.02 57.28 40.13 marlstone 39 335 Magnesitic 1.79 36.09 3.38 0.06 195.15 0.42 2.11 0.06 13.48 2.11 0.02 1.79 0.90 marlstone 40 336 Magnesitic 1.88 35.78 1.57 0.02 58.46 0.84 3.14 0.28 14.30 2.10 0.02 7.55 3.92 marlstone 41 340 Mg-clay 9.76 674.9411.17 0.11 1144.50 0.98 20.60 1.51 2.96 1.90 0.02 32.56 19.45 42 341 Mg-clay 11.94 995.59 11.51 0.13 1705.72 1.74 23.89 2.37 2.93 2.22 0.02 39.38 24.52

5 TABLE S-I. Continued Sample Depth CPa CIWb Litology As Cr Cu Hg Ni Pb Zn Al O CaO Na O P O No. m 2 3 2 2 5 % % 43 343 Mg-clay 1.73 1397.25 27.12 0.13 2420.53 4.00 44.30 4.39 0.68 2.12 0.02 55.73 55.58 Local background valuesc 5.79 113.14 7.21 0.04 165.69 2.54 12.38 1.75 19.12 0.86 0.01 – – RS 50/201218 29 100 36 0.30 35.0 85.0 140 – – – – – – FBiH 72/0919 25 125 100 1.88 62.5 125.0 250 – – – – – – ÖNORM S 2088-220 20 100 100 1.00 60.0 100.0 300 – – – – – – PELd 17 90 108 0.49 – 91.3 271 – – – – – – a 15 b 6 Chemical Proxy of Alteration; CPA = 100Al2O3/(Al2O3 + Na2O), all oxides are expressed in mole proportions; Chemical Index of Weathering; CIW = 16 7 = 100Al2O3/(Al2O3 + CaO* + Na2O), where CaO* represents Ca in the silicate-bearing minerals only and all oxides are expressed in mole proportions. The 8 procedure for quantification of CaO content of silicate fraction involves subtraction of mole proportion of P2O5 from the molar proportion of total CaO. On subtraction, 9 if the “remaining number of moles” is found to be less than the molar proportion of Na2O, then the “remaining number of moles” is considered as the molar proportion 10 of CaO of silicate fraction. If the “remaining number of moles” is greater than the molar proportion of Na2O, then the molar proportion of Na2O is taken as the mole 11 proportion of CaO of silicate fraction;17 cfor every element mean ±2 standard deviation were used to eliminate the top and bottom outlying data;13 dProbable Effect 12 Level (PEL) characterizes the concentrations of pollutants that may affect the aquatic life21,22

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